Internally plasticized melamine resins



United States Patent ,Ofiice 2,916,410 Patented Dec. 8, 1959 INTERNALLY PLASTICIZED MELAMINE RESINS George L. Fraser, Wiibraham, and Curtis Elmer, Springfield, Mass., assignors to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application November 12, 1953 Serial No. 391,746

11 Claims. (Cl. 154-43) This invention relates to internally plasticized melamine resins. More particularly, this invention relates to internally plasticized melamine resins that can be used to prepare post-formable laminates.

Melamine-aldehyde resins comprise a well-known class of thermosetting compositions useful for many purposes such as the preparation of surface coatings, molding powders, adhesives, laminating syrups, etc. Unmodified melamine resins have relatively poor flow properties during curing operations and this has created a serious prob- .lem. It has been proposed to mix melamine resms with flow promoting agents such as polyesters, polyethylene glycols, etc. which do not chemically combine with the melamine resin. Flow promoting agents of this nature are commonly referred to as external plasticizers and are most advantageously used in preparing non-aqueous compositions such as baking enamels, adhesives, etc.

Most conventional external plasticizers are either waterinsoluble or incompatible with melamine resins in aqueous solutions and, accordingly, cannot be used successfully in preparing compositions comprising aqueous solutions of a melamine-aldehyde resin. When aqueous solutions: of this nature are to be prepared, it is common practice to use an internal plasticizer which is chemically com bined in the melamine resin. Thus, compounds such as aromatic sulfonamides, aromatic amines, aromatic amides,

etc. may be reacted with melamine and an aldehyde toform internally plasticized resins that can be dissolved in water without adverse effects. Internally plasticized melamine resins of this nature are commonly used in the preparation of laminating syrups which comprise a solution of the resin in water or a mixture of water with a lower aliphatic alcohol. Such laminating syrups are particularly useful in the preparation of decorative laminates having high surface gloss coupled with excellent chemical and physical resistance properties. However, conventional laminates of this nature have generally proved unsatisfactory for post-forming operations wherein the laminate is heated and bent about a form into a different shape.

Accordingly, an object of the present invention is the provision of internally plasticized melamine resins.

Another object is the provision of internally plasticized melamine resins that can be used to prepare post-formable laminates.

These and other objects are attained by co-condensing melamine with formaldehyde or a polymer thereof and a member of a restricted class of omega cyanoalkyl guanamines as hereinafter defined.

The following examples are given by way of illustration and are not intended as limitations on the scope of this invention. Where parts are mentioned, they are parts by weight. 5

Example I Mix 100 parts of melamine with 200 parts of a 37% aqueous solution of formaldehyde and adjust the pH of the mixture to about 9.5 to 10.0 with an aqueous soluamine resin-impregnated alpha-cellulose.

tion of sodium hydroxide. Heat the mixture to a temperature of about C. in order to initiate a condensation reaction between the melamine and the formaldehyde. As soon as the reaction has been initiated, add 40 parts of omega-cyanovaleroguanamine (2-cyanobutyl-4,6- diamino-l,3,5-triazine) and then continue the reaction at a temperature of 90 C. for about 4 hours. Stop the reaction by cooling the reaction mixture when the cocondensation product has a 25% water dilutability (i.e. when an aqueous solution of the co-condensation product can be reduced to a 25 solids solution without precipitation of the resin). About 20% by weight of the co-condensation product formed as a result of this reaction is derived from the omega-cyanovaleroguanarnine. Dilute the co-condensation product with water to form a 50% solids solution thereof which is useful as a laminating syrup.

Example II Dip sheets of alpha-cellulose in the laminating syrup of Example I and remove the sheets slowly therefrom at a rate such that the impregnated sheets comprise about 65% by weight of resin on a dry weight basis. Dry the sheets at C. until the volatile content of the sheets is less than 5%. This will normally require less than one half hour. Assemble a plurality of such sheets to form a sandwich and mold the sandwich at a pressure of about 1,000 psi. and a temperature of about C. for about 15 minutes. Remove the laminate from the mold and cool. The laminate so produced has an attractive appearance, high surface gloss and good chemical and physical resistance properties. Heat a section of the cooled laminate to a temperature of about -170 C. and then form the heated section about a inch mandrel to produce a 90 bend. Cool the laminate about the mandrel and then remove. The laminate maintains the curved shape and possesses all of the propert es that it had prior to the post-forming operation with special reference to surface appearance and gloss, which is unimpaired. There is no evidence of crazing, cracking or delamination.

As another example, prepare a sandwich comprising a core of sheets of kraft paper and crepe paper impregnated with a post-formable .cresol-formaldehyde resin, and cover sheets of the above-described modified mel- Form a laminate by pressing the sandwich at a pressure of about 1,000 p.s.i. and a temperature of about 140 C. for about Example III Add 100 parts of melamine to 200 parts of a 37% aqueous solution of formaldehyde and adjust the pH of the mixture to about 9.510.0 with an aqueous solution of sodium hydroxide. Heat to a temperature of about 80 C. and add 50 parts of omega-cyanopropioguanamine (2 cyanoethyl 4,6 diamino 1,3,5 triazine). Maintain this mixture at a temperature of about 85-90 C. for about four hours to form a co-condensation product. Terminate the reaction by cooling the reaction mixture when the co-condensation product has a 20% Water dilutability. A syrupy aqueous solution of the cocondensation product isv obtained, about 25% by weight of the co-condensation product being derived from the gu'anamine. Spray dry the aqueous syrup to obtain a pulverulent material which may be readily dispersed in water. The powder is fusible and may be cured under heat and pressure to an insoluble infusible state. Laminate two pieces of wood by placing between the pieces a thin layer ofthe powder followed by heating the sandwich at 150 C. for 10 minutes at 500 p.s.i. During the laminating step the resin flows readily to form a thin continuous film which penetrates the fibers of the wood and bonds the pieces of wood together.

The powder can be dissolved in water or a mixture comprising a major amount of water and a minor amount of a lower aliphatic alcohol in order to form a laminating syrup. The laminating syrup can be used to prepare post-formable laminates similar to the laminates of Example II.

Equally satisfactory results are obtained when the omega-cyanopropioguanamine is replaced by an equimolar amount of 4-N ethyl-omega-cyanovaleroguanamine (2 cyanobutyl 4 ethylamino 6 amino 1,3,5- triazine) or an equimolar amount of 4-N phenyl-cyanoacetoguanamine (2-cyanomethyl-4-phenylamino-6-amino 1,3,5-triazine) and the example is otherwise repeated in the described manner. In each instance a post-formable co-condensation product of melamine, formaldehyde and guanamine is formed.

Example IV Mix together 100 parts of melamine, 250 parts of a 37% aqueous solution of formaldehyde and 30 parts of omega-cyanononoguanamine (Z-cyanooctyl-4,6-diamino- 1,3,5-triazine). Adjust the pH of the mixture to about 9.510.0 with an aqueous solution of sodium hydroxide. Heat the mixture at a temperature of about 90 C. to form a resinous co-condensation product, terminating the reaction by cooling the reaction mixture when a sample of the co-condensation product has a C. hydrophobe point (i.e. when the co-condensation product is hydrophilic with respect to water at a temperature of 5 C. or higher but hydrophobic with respect to water at a temperature of less than 5 C.). A syrupy aqueous solution of the co-condensation product is obtained, about 15% by weight of the co-condensation product being derived from the guanamine. Spray dry the aqueous syrup to obtain a powdered resin. Blend 100 parts of the powder with 100 parts of Wood flour and mold the blend under heat and pressure to form a solid unitary article. A pressure of from 100 to 6,000 p.s.i. and a temperature of from 100-250 C. may be used. On

removal from the mold, the article is found to have high gloss and excellent chemical and physical resistance properties. The resin substantially completely surrounds and impregnates the filler to give a homogeneous product.

The powdered co-condensation product can be dissolved in water or a mixture of a major amount of water and a minor amount of a lower aliphatic alcohol to form a laminating syrup. The laminating syrup can be used to prepare post-formable laminates similar to the laminates of Example II.

The resins of the present invention are co-condensation products of melamine, formaldehyde or a polymer thereof and a particular class of cyanoalkyl guanamines that act as internal platicizers. The guanamines to be used in accordance with the present invention have the formula wherein n is an integer of 1-8 inclusive and the Rs are the same or different and are taken from the group con- .4 sisting of hydrogen, unsubstituted phenyl radicals, methyl and halogen nuclearly substituted phenyl radicals, and alkyl radicals having 1-8 carbon atoms inclusive, at least one of the Rs being hydrogen and not more than one of the Rs being taken from the group consisting of substituted and unsubstituted phenyl radicals. That is to say, the Rs taken together are members of the group consisting of hydrogen and heterologous mixtures of hydrogen, unsubstituted phenyl radicals, halogen and methyl nuclearly substituted phenyl radicals, and alkyl radicals having 1-8 carbon atoms inclusive, at least one of the Rs of said heterologous mixtures being hydrogen and not more than one of the Rs being taken from the group consisting of substituted and unsubstituted phenyl radicals. Reference to a compound containing a heterologous mixture of radicals is a method of defining a guanamine of the above formula wherein the Rs are not all the same. The halogenmay be chlorine, bromine, fluorine or iodine.

Illustrative of the guanamines of the present invention are cyanoacetoguanamine (2-cyanomethyl-4,6-diamino- 1,3,5-triazine), omega-cyanopropioguanamine (Z-cyanoethyl 4,6 diamino 1,3,5 triazine), omega cyanovaleroguanamine (Z-cyanobutyl-4,6-diamino-1,3,5-triazine), omega-cyanononoguanamine (2-cyano octyl-4,6-diamino- 1,3,5 -triazine) 4-N methyl-omega-cyanovaleroguanamine (2-cyanobutyl-4-methylamino-6-amino-1,3,5-triazine), 4- N-ethyl-omegacyanovaleroguanamine (2-cyanobutyl-4- ethylamino-6-amino-l,3,5-triazine), 4,6-dimethyl-omegacyanovaleroguanamine (2-cyanobutyl-4,6-methylamino- 1,3,5-triazine), 4-N hexyl-omega-cyanopropioguanamine (2-cyanoethyl-4-hexylamino-6-amino-l,3,5-triazine), 4-N octyl cyanoacetoguanamine (2 cyanornethyl 4 octylamino-6-amino-l,3,5-triazine), 4-N phenyl cyanoacetoguanamine (Z-cyanomethyl 4 phenylamino 6 amino- 1,3,5-triazine), 4-N tolyl cyanoacetoguanamine (2-cyanomethyl-4-tolylamino-6-amino-1,3,5-triazine), 2 (omegacyanopropio) 4 (orthochlorphenyl)amino 6 amino- 1,3,5 triazine, 2 (omega cyanoethyl) 4 (2,5- dichlorphenyl)amino-6-amino-1,3,5-triazine, etc. Mixtures of two or more such guanamines may be used if desired. The well-known methods such as those described in US. Patent No. 2,394,526 to Thurston and British Patent No. 642,409 may be used to prepare the guanamines that are used as starting materials in accordance with the present invention.

The amount of formaldehyde to be reacted with the melamine will vary, depending on the final use for which the resin is intended. If desired, an equivalent amount of a polymer of formaldehyde such as paraformaldehyde, trioxymethylene, etc. may be used in place of part or all of the formaldehyde. Generally speaking, the amount of formaldehyde or polymer thereof to be used should be such that from about 1-6 equivalents of aldehyde radical are present for each mol of melamine.

Since the omega-cyanoalkyl guanamines of the present invention function primarily as internal plasticizers, the amount to be used will vary depending upon the amount of formaldehyde reacted with the melamine, the extent to which the melamine resin is to be plasticized, the compatibility of the guanamine with the melamine and formaldehyde, etc. Generally speaking, it is preferable to use less than one mol of guanamine per mol of melamine and to use an amount of guanamine such that about 10-35% by weight of the co-condensation product is derived from the omega-cyanoalkyl guanamine. As a general rule, if from about to mol of omega-cyano alkyl guanamine per mol of melamine is used, the de sired amount of omega-cyanoalkyl guanamine derivative will be present in the co-condensation product and the resultant resin will be post-formable.

The reaction between the melamine, the omega-cyanoalkyl guanamine and formaldehyde should be carried out at a pH of 8-12 and preferably at a pH of 9-11. The

pH of the reaction mixture is conveniently adjusted with an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide, benzyl trirnethyl ammonium hydroxide, choline etc. The temperature of the reaction may be varied from about 40 C. to reflux temperature at atmospheric pressure. For purposes of accurate control of reaction rate and in order to control the properties of the reaction product, it is preferable to conduct the reaction at a temperature of about 80-100 C. for the greater part of the reaction time. A convenient procedure is that shown in Example I wherein a mixture of melamine and formaldehyde is brought to reaction temperature in order to initiate reaction, at which time the omega-cyanoalkyl guanamine is added. However, if desired, the guanamine may be admixed with melamine and formaldehyde prior to the reaction, as shown in Example IV. The omega-cyanoalkyl guanamine may also be added after the melamine and formaldehyde have been partially condensed. However, the omega-cyanoalkyl guanamines of the present invention are internal plasticizers which should be reacted in with the melamine and formaldehyde to form a co-condensation product. Accordingly, if delayed addition of the omega-cyanoalkyl guanamine is resorted to, the delay in addition should not be so prolonged that the guanamine does not have an opportunity to substantially completely react.

The resinous co-condensation products of the present .invention, while still in a fusible condition, are preferably compounded with suitable inert fillers in order to increase the strength of articles formed therefrom. Thus, for example, the resin may be dried, comminuted and mixed with a finely divided filler in order to form a molding powder or the resin may be dissolved in a suitable solvent to form a laminating syrup for impregnating a sheeted filler. Among the inert fillers that may be used are glass, asbestos, paper, wood flour, cellulose, etc. The filled fusible resin can be formed into articles of utility by suitable molding processes wherein the resin is converted to a substantially insoluble infusible condition through the application of heat and pressure.

The laminating syrups of the present invention are preferably aqueous solutions of amorphous co-condensation products which are still water-soluble and fusible. Under some conditions it is desirable to add to the water a monohydroxy aliphatic alcohol having 1-4 carbon atoms (e.g. methanol, ethanol, propanol or butanol), especially if the condensation reaction has proceeded so far that the resin is more soluble in the alcohol than the water. When an alcohol is used, it should preferably comprise less than 50% by weight of the alcohol- Water mixture.

Satisfactory laminating syrups comprise from about 4060% by weight of co-condensation product. The amount of co-condensation product to be used is, in part, dependent upon the extent to which a sheet of filler is to be impregnated. Sheet materials useful as fillers may be prepared from separable formable elements by felting or weaving processes. Among the materials that have proven adaptable are paper, textiles such as cotton, nylon, etc., glass cloth and batts, alpha-cellulose, etc. In preparing laminates, the core may comprise a composition quite different from the surface sheet or overlay. The high gloss and superior flow properties of the resins of this invention make them especially suitable as binders for overlay sheets, particularly where the overlay sheet is laminated over a decorative surface. The co-condensation products of the present invention can be post-formed without material impairment of chemical and physical properties. Accordingly, when the laminates are to be post-formed, it is usually preferable to use an inexpensive core material that may also be subjected to post-forming operations. Suitable core materials include fillers bonded with post-formable phenolic resins such as post-formable phenol-formaldehyde, cresol-formaldehyde, cresol-phenolformaldehyde, etc. resins.

The fusible co-condensation products of the present invention maybe cured to an insoluble infusible state by being heated at a temperature of from IOU-250 C. It is not necessary to use a curing catalyst but a suitable catalyst may be used if desired. Pressures of at least 50 psi. should be used if a dense, non-porous product is to be obtained.

In conducting post-forming operations, the portion of the laminate to be shaped should preferably be heated to within a few degrees of the blistering temperature of the laminate and formed into the desired shape immediately thereafter. The shaped section is preferably permitted to cool before being removed from the form. The temperature to be used and the time for which the laminate is to be heated are dependent on the thickness of the laminate, the nature of the core material, the extent to which the laminate is to be post-formed, etc. It is usually necessary to heat the portion of the laminate to be post-formed to a temperature of C. or higher in order to obtain satisfactory results.

What is claimed is:

1. A heat-hardenable internally plasticized resinous co-condensation product of 1 mol of melamine, l-6 mols of an aldehyde taken from the group consisting of formaldehyde and polymers thereof and 0.05 to 0.25 mol of an omega-cyanoalkyl guanamine having the formula:

wherein n is an integer of from 1 to 8 and R and R are independently selected from the group consisting of hydrogen and methyl, ethyl and phenyl radicals.

2. A resinous co-condensation product as in claim 1 wherein the omega-cyanoalkyl guanamine is omegacyanovaleroguanamine.

3. A resinous co-condensation product as in claim 1 wherein the omega-cyanoalkyl guanamine is omegacyanopropioguanamine.

4. A resinous co-condensation product as in claim 1 wherein the omega-cyanoalkylguanamine is omega-cyanononoguanamine.

5. A laminating syrup comprising from 40-60% by Weight of a post-formable co-cond'ensation product of 1 mol of melamine, 24 mols of an aldehyde taken from the group consisting of formaldehyde and polymers thereof and 0.05 to 0.25 mol of an omega-cyanoalkylguanamine in solution in from 60-40% by weight of a solvent taken from the group consisting of water and mixtures of a major amount of water and a minor amount of a monohydric aliphatic alcohol having from 1 to 4 carbon atoms, said omega-cyanoalkylguanamine having the formula:

wherein n is an integer of from 1 to 8 and R and R are independently selected from the group consisting of hydrogen and methyl, ethyl and phenyl radicals.

6. A laminating syrup containing a 50% solids aqueous solution of a co-condensation product of 1 mol of melamine, about 3 mols of formaldehyde and 0.05 to 0.25 mol of omega-cyanovaleroguanamine.

7. A laminating syrup comprising a 50% solids aqueous solution of a co-condensation product of 1 mol of wherein n is an integer of from 1 to 8 and R and R are independently selected from the group consisting of hydrogen and methyl, ethyl and phenyl radicals.

10. A normally rigid post-formable laminate comprising a sheeted inert filler bonded with a thermoset cocondensation product of 1 mol of melamine, 2-4 mols of formaldehyde and 0.05 to 0.25 mol of an omegacyanoalkylguanamine having the formula:

wherein n is an integer of from 1 to 8 and R and R are independently selected from the group consisting of hydrogen and methyl, ethyl and phenyl radicals.

11. A normally rigid post-formable laminate comprising a cover sheet of inert filler bonded to a post-formable core material by a thermoset post-formable co-condensation product of 1 mol of melamine, 2-4 mols of formaldehyde and 0.05 to 0.25 mol of an omega-cyanoalkylguanamine having the formula:

CN (C iHzh ('1 H N% \N H wherein n is an integer of from 1 to 8 and R and R are independently selected from the group consisting of hydrogen and methyl, ethyl and phenyl radicals.

5 References Cited in the file of this patent UNITED STATES PATENTS 2,286,228 Ripper June 16, 1942 2,331,446 Widmer et al. Oct. 12, 1943 2,368,451 DAlelio Ian. 30, 1945 2,439,929 Hill et al. Apr. 20, 1948 2,548,772 Castle Apr. 10, 1951 2,579,985 Varela et al. Dec. 25, 1951 2,635,083 Cordier Apr. 14, 1953 2,652,375 Cordier et al Sept. 15, 1953 

10. A NORMALLY RIGID POST-FORMABLE LAMINATE COMPRISING A SHEETED INERT FILLER BONDED WITH A THERMOSET COCONDENSATION PRODUCT OF 1 MOL OF MELAMINE, 2-4 MOLS OF FORMALDEHYDE AND 0.05 TO 0.25 MOL OF AN OMEGACYANOALKYLGUANAMINE HAVING THE FORMULA: 